CN102180815A - Process for producing benzene-m-disulfonic acid by using gas-phase sulfonation method - Google Patents
Process for producing benzene-m-disulfonic acid by using gas-phase sulfonation method Download PDFInfo
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- CN102180815A CN102180815A CN2011100711495A CN201110071149A CN102180815A CN 102180815 A CN102180815 A CN 102180815A CN 2011100711495 A CN2011100711495 A CN 2011100711495A CN 201110071149 A CN201110071149 A CN 201110071149A CN 102180815 A CN102180815 A CN 102180815A
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Abstract
The invention discloses a process for producing benzene-m-disulfonic acid by using a gas-phase sulfonation method, and relates to a process for producing benzene-m-disulfonic acid by using a continuous gas-phase sulfonation method, which solves the problems that a large amount of high-concentration waste acid can be produced in the production process of benzene-m-disulfonic acid, and the like in the prior art. The concrete process comprises the following steps: gaseous sulfur trioxide used as a sulfonating agent and benzene enter a novel sulfonation reactor for primary sulfonation reaction, with the mole ratio of the benzene to the sulfur trioxide controlled to be 1:1-1.2, and the temperature controlled to be 20-100 DEG C; gaseous sulfur trioxide is continuously introduced into primary sulfonation materials for secondary sulfonation reaction, with the mole ratio controlled to be 1:1-1.3, and the temperature controlled to be 120-180 DEG C, and the addition amount of an inhibitor sodium 1,3-benzenedisulfate is 2-16% of the weight of the benzene and the sulfur trioxide. Original fuming sulfuric acid is replaced to enable the sulfonation materials not to contain a large amount of strong acid, so as to save alkali raw materials; continuous production and automation production are realized; and the sodium 1,3-benzenedisulfate is used for replacing sodium sulfate as the inhibitor, so as to reduce the yield of the sodium sulfate in the neutralization reaction process and the production of solid wastes.
Description
Technical field:
The present invention relates to the production technique of benzene disulfonic acid between the production of gas phase xanthation method.
Background technology:
Resorcinol is a kind of important fine chemistry industry organic raw material, is widely used in rubber, plastics, medicine, agricultural chemicals, dye well electron chemistry product.Wherein be mainly used in tire fabric impregnation, use for synthetic rubber tacky resin, wood gluing plate with high performance tackiness agent, organic intermediate amino phenol and benzophenone UV light absorber.The technology of at present the most traditional in the world production Resorcinol is sulfonated alkali fusion method, the most of enterprises that comprise states such as China, the U.S., India, Russia all adopt this method production, the production technique of Resorcinol: the sulfonation under the effect of catalyzer of benzene and oleum, neutralization, alkali fusion, acidifying, distill finished product.Its technical process is followed successively by: sulfonation, neutralization, alkali fusion, acidifying, distillation, finished product.At present sulfonated alkali fusion method is produced the problem that the technology of Resorcinol mainly exists: old-fashioned sulfonating reaction process is that the oleum with benzene and 65% carries out sulfonation, sulfonation material and 25% sodium hydroxide solution carry out neutralization reaction, because there is a large amount of sulfuric acid in the sulfonated products, need a large amount of highly basic to neutralize, with producing the useless admittedly and waste liquid of a large amount of inorganic salt.1 ton of Resorcinol of every production need consume 7 tons in sodium hydroxide, and 12 tons of 30% hydrochloric acid produce 2 tons in sodium sulfate, and 5 tons of S-WATs approximately discharge high density saliferous, phenol waste water 15M
3, these treating waste liquid difficulty are bigger, and processing costs is than higher, seriously polluted to environment.
Chinese patent CN1970520 discloses a kind of clean resorcinol production method, being raw material with benzene, and through oversulfonate, neutralization, alkali is molten, and processes such as acidifying are produced Resorcinol, and this method adopts saltcake acid as nitrating agent, acid consumption is big, and is higher to equipment requirements, and environmental pollution is comparatively serious.
Disclose a kind of new clean resorcinol production method among the patent CN101643391A, adopted SO
3Enter into as sulphonating agent and benzene and to spray annular reactor and react, this method is few with the acid amount, the byproduct NaCl that obtains enters other workshop recycle, both economical, but this method adopts air as thinner, oxidisability height, reaction system have the danger of blast, consider inadvisable from security standpoint.
Summary of the invention:
The present invention is in order to solve in the Resorcinol sulfonation production process, and a large amount of vitriolic use the acid-treated problem of bringing.
Problems such as the present invention is also huge in order to solve reaction unit equipment, and heat transfer efficiency is low, production process is discontinuous provide a kind of technology of Resorcinol sulfonation material.
Benzene disulfonic acid production technique between a kind of gas phase xanthation method is produced, its step is as follows:
(1) liquid sulphur trioxide in the sulphur trioxide test tank enters into sulfonation reactor by vaporizer and rare gas element, the benzene test tank enters into sulfonation reactor and gaseous sulfur trioxide reaction, the mol ratio of benzene and sulphur trioxide is 1:1～1.2, temperature is 40～90 ℃, and the sodium 1,3-benzenedisulfate by feeder for solid materials is an inhibitor;
The gas mixture that feeds sulphur trioxide and rare gas element in (2) one sulfonated products carries out two sulfonation reactions, and mol ratio is controlled at 1:1～1.3, and temperature is controlled at 120～180 ℃, and behind reaction times 3～8 h, reaction mass enters the aging reaction still;
(3) reaction mass in the aging reaction still, continue reaction behind 2～12 h between benzene disulfonic acid.
Described inhibitor sodium 1,3-benzenedisulfate add-on is 2～16% of benzene and a sulphur trioxide weight.
The molar ratio of benzene and sulphur trioxide is 1:2～2.5 in the step (1).
The material that ventilation is finished need continue to react 2～12 hours.
Step (1) temperature of reaction is 50～70 ℃; 140～160 ℃ of step (2) temperature of reaction.
Described rare gas element is one or several the gas mixture in nitrogen, carbonic acid gas, the rare gas.
The rare gas element that adopts and the blending ratio of sulphur trioxide are 1:1～48:1.
The present invention adopts following technical scheme to realize: the production technique of benzene disulfonic acid between a kind of serialization gas phase xanthation method is produced, produce problems such as a large amount of high density spent acid between solution is existing in the benzene disulfonic acid production process, make sulphonating agent and benzene carries out sulfonation reaction with gaseous sulfur trioxide, total molar ratio is controlled between 1:2～2.5.Detailed process is to do sulphonating agent and benzene with gaseous sulfur trioxide to enter and carry out a sulfonation reaction in the novel sulfonated reactor, and the mol ratio of benzene and sulphur trioxide is controlled at 1:1～1.2, and temperature is controlled at 20～100 ℃; Continue to feed the gasiform sulphur trioxide in the one sulfonation material and carry out two sulfonation reactions, mol ratio is controlled at 1:1～1.3, and temperature is controlled at 120～180 ℃, and the add-on of inhibitor sodium 1,3-benzenedisulfate is 2～16% of benzene and a sulphur trioxide weight.
Compared with prior art, the present invention has the following advantages:
(1) replaces original oleum with sulphur trioxide, made the sulfonation material of production not contain a large amount of strong acid, saved the raw-material usage quantity of alkali.
(2) utilize the recycled of material, the charging capacity of the material of minimizing has realized that a sulfonation, two sulfonated serializations produce, and automatic production reduces labour intensity and labor force.
(3) transformation efficiency of benzene disulfonic acid is 96-98% between.
(4) replace sodium sulfate to make inhibitor with sodium 1,3-benzenedisulfate, reduced the output of sodium sulfate in the neutralization reaction process, greatly reduce the generation of solid waste.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention
Among the figure: 1-benzene test tank 2-benzene pump 3-one-level sulfonation reactor 4-one-level sulfonation reaction still
5-one-level sulphur recycle pump 6-sulphur trioxide test tank 7-vaporizer 8-sulphur trioxide test tank
9-vaporizer 10-secondary sulfonation reactor 11-secondary sulfonation reaction still 12-secondary sulphur recycle pump
13-aging reaction still 14-feeder for solid materials
Embodiment:
The following example further specifies this technology
Embodiment 1
In 3000L one-level sulfonation reaction still 4, add 800L sulfonation material, transferring the add-on of feeder for solid materials 14 sodium 1,3-benzenedisulfates is 3 kg/h, add to open and stir and recycle pump 5, control one-level sulfonation reactor 3 temperature are at 40 ℃, transferring one-level sulphur recycle pump 5 flows is 0.65m3/h, add benzene by benzene test tank 1 in one-level sulfonation reactor 3, it is 89L/h that adjustment benzene pump 2 makes the benzene flow, and the sulfonation material dilutes benzene; Liquid sulphur trioxide in the sulphur trioxide test tank 6 advances vaporizer 7 vaporizations, mixes entering sulfonation reactor 3 again, SO in the mixed gas with nitrogen
3Content is 10%, and flow is 224L/h.Begin to overflow to after 5 hours in the secondary sulfonation reaction still 11, after 4 hours, control secondary sulfonation reactor 10 temperature are at 120 ℃, driving secondary sulfonation reaction still 11 stirs and secondary sulphur recycle pump 12, liquid sulphur trioxide in the sulphur trioxide test tank 8 enters vaporizer 9 vaporization backs and mixes SO in the mixed gas with nitrogen
3Content is 10%,, SO
3Flow is 224L/h, and aging reaction still 13 is advanced in overflow behind the 4.5h, continues operation 15～20 hours, the sampling analysis quality product.
Analytical results: aging still sampling
Embodiment 2
In 3000L one-level sulfonation reaction still 4, add 800L sulfonation material, transferring the add-on of feeder for solid materials 14 sodium 1,3-benzenedisulfates is 29.1kg/h, open and stir and recycle pump 5, control one-level sulfonation reactor 3 temperature are at 90 ℃, transferring one-level sulphur pump flow is 0.6m3/h, add benzene by benzene test tank 1 in one-level sulfonation reactor 3, it is 89 L/h that adjustment benzene pump 2 makes the benzene flow, and the sulfonation material dilutes benzene; Liquid sulphur trioxide in the sulphur trioxide test tank 6 advances vaporizer 7 vaporizations, enters sulfonation reactor 3 again with carbon dioxide mix, and SO3 content is 30% in the mixed gas, and flow is 89.6 L/h.Begin to overflow to after 5 hours in the secondary sulfonation reaction still 11, after 4 hours, control secondary sulfonation reactor 10 temperature are at 180 ℃, drive secondary sulfonation reaction still and stir and secondary sulphur recycle pump 12, the liquid sulphur trioxide in the sulphur trioxide test tank 8 advances vaporizer 9 vaporization back and carbon dioxide mix, and SO3 content is 30% in the mixed gas, the SO3 flow is 97.1 L/h, 4.5h aging reaction still 13 is advanced in back overflow, continues operation 10～15 hours, the sampling analysis quality product.
Analytical results: aging still sampling
Embodiment 3
In 3000L one-level sulfonation reaction still 4, add 800L sulfonation material, transferring the add-on of feeder for solid materials 14 sodium 1,3-benzenedisulfates is 20kg/h, add to open and stir and recycle pump 5, control one-level sulfonation reactor 3 temperature are at 50 ℃, transferring one-level sulphur pump flow is 0.6m3/h, add benzene by benzene test tank 1 in one-level sulfonation reactor 3, it is 100L/h that adjustment benzene pump 2 makes the benzene flow, and the sulfonation material dilutes benzene; Liquid sulphur trioxide in the sulphur trioxide test tank 6 advances vaporizer 7 vaporizations, mixes entering sulfonation reactor 3 again with nitrogen, and SO3 content is 15% in the mixed gas, and flow is 90 L/h.Begin to overflow to after 4 hours in the secondary sulfonation reaction still 11, after 2 hours, control secondary sulfonation reactor 10 temperature are at 150 ℃, drive secondary sulfonation reaction still and stir and secondary sulphur recycle pump 12, the liquid sulphur trioxide in the sulphur trioxide test tank 8 enters vaporizer 9 vaporization backs to be mixed with rare gas element, and SO3 content is 15% in the mixed gas, the SO3 flow is 100L/h, 4.5h aging reaction still 13 is advanced in back overflow, continues operation 20～25 hours, the sampling analysis quality product.
Analytical results: aging still sampling
Claims (8)
1. benzene disulfonic acid production technique between a gas phase xanthation method is produced is characterized in that:
(1) in one-level sulfonation reaction still (4), adds the sulfonation material, the inhibitor sodium 1,3-benzenedisulfate adds by feeder for solid materials (14), the sulfonation material in the sulfonation reaction still (4) by a sulfonation pump (5) circulation with enter that sulfonation reaction still (4) is middle to react after benzene, gaseous sulfur trioxide in the benzene test tank (1) mixes again;
(2) product in the one-level sulfonation reaction still (4) enters into secondary sulfonation reaction still (11), and product is mixed into secondary sulfonation reaction still (11) reaction by the circulation of two sulfonation pumps (12) with gaseous sulfur trioxide, rare gas element;
(3) reaction mass in aging reaction still (13), continue reaction behind 2～12 h between benzene disulfonic acid.
2. production technique according to claim 1 is characterized in that: the mol ratio of benzene and sulphur trioxide is 1:1～2.5 in the step (1), and temperature is 40～90 ℃.
3. production technique according to claim 1 is characterized in that: the temperature in the step (1) is 50～70 ℃.
4. production technique according to claim 1 is characterized in that: described inhibitor sodium 1,3-benzenedisulfate add-on is 2～16 % of benzene and sulphur trioxide weight.
5. production technique according to claim 1 is characterized in that: step (2) one sulfonated products and rare gas element mol ratio be controlled at 1:1～1.3, temperature is 120～180 ℃.
6. production technique according to claim 1 is characterized in that: the temperature of step (2) is 140～160 ℃.
7. production technique according to claim 1 is characterized in that: described rare gas element is one or several the gas mixture in nitrogen, carbonic acid gas, the rare gas.
8. production technique according to claim 1 is characterized in that: the rare gas element of employing and the blending ratio of sulphur trioxide are 1:1～48:1.
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| CN 201110071149 CN102180815B (en) | 2011-03-23 | 2011-03-23 | Process for producing benzene-m-disulfonic acid by using gas-phase sulfonation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816092A (en) * | 2012-08-31 | 2012-12-12 | 江苏中丹集团股份有限公司 | Device for continuously preparing m-benzenedisulfonic acid |
| CN104474986A (en) * | 2014-11-11 | 2015-04-01 | 王孝通 | Gas sulfur trioxide continuous sulfonation production device |
| CN109351316A (en) * | 2018-12-22 | 2019-02-19 | 山东大明精细化工有限公司 | It is a kind of for producing the tank reactor and its application method of surfactant |
| CN110526840A (en) * | 2019-09-19 | 2019-12-03 | 南雄市汉科化工科技有限公司 | Synthesize the preparation process and reaction unit of dodecyl Biphenyl Ether disulfonic acid sodium salt |
| CN114835612A (en) * | 2022-03-11 | 2022-08-02 | 青岛科技大学 | Synthetic method for preparing m-aminophenol |
| CN114950320A (en) * | 2022-05-31 | 2022-08-30 | 浙江巨化技术中心有限公司 | Device and method for continuously synthesizing tetrafluoroethane-beta-sultone |
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| US3941810A (en) * | 1972-10-30 | 1976-03-02 | Adolf Koebner | Sulfonation of aromatic compounds in the presence of solvents |
| WO1988001617A1 (en) * | 1986-09-05 | 1988-03-10 | Amoco Corporation | Improvement for processes for preparing diaryl sulfones |
| CN101723858A (en) * | 2008-10-17 | 2010-06-09 | 南化集团研究院 | Method for preparing benzenesulfonic acid |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3941810A (en) * | 1972-10-30 | 1976-03-02 | Adolf Koebner | Sulfonation of aromatic compounds in the presence of solvents |
| WO1988001617A1 (en) * | 1986-09-05 | 1988-03-10 | Amoco Corporation | Improvement for processes for preparing diaryl sulfones |
| CN101723858A (en) * | 2008-10-17 | 2010-06-09 | 南化集团研究院 | Method for preparing benzenesulfonic acid |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816092A (en) * | 2012-08-31 | 2012-12-12 | 江苏中丹集团股份有限公司 | Device for continuously preparing m-benzenedisulfonic acid |
| CN104474986A (en) * | 2014-11-11 | 2015-04-01 | 王孝通 | Gas sulfur trioxide continuous sulfonation production device |
| CN109351316A (en) * | 2018-12-22 | 2019-02-19 | 山东大明精细化工有限公司 | It is a kind of for producing the tank reactor and its application method of surfactant |
| CN110526840A (en) * | 2019-09-19 | 2019-12-03 | 南雄市汉科化工科技有限公司 | Synthesize the preparation process and reaction unit of dodecyl Biphenyl Ether disulfonic acid sodium salt |
| CN114835612A (en) * | 2022-03-11 | 2022-08-02 | 青岛科技大学 | Synthetic method for preparing m-aminophenol |
| CN114950320A (en) * | 2022-05-31 | 2022-08-30 | 浙江巨化技术中心有限公司 | Device and method for continuously synthesizing tetrafluoroethane-beta-sultone |
| CN114950320B (en) * | 2022-05-31 | 2023-09-15 | 浙江巨化技术中心有限公司 | Device and method for continuously synthesizing tetrafluoroethane-beta-sultone |
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| CN102180815B (en) | 2013-02-27 |
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Effective date of registration: 20150615 Address after: 225453, No. 8, Tongjiang Road, Yanjiang Economic Development Zone, Taixing, Jiangsu, Taizhou Patentee after: Jiangsu Zhongdan Chemical Technology Co., Ltd. Address before: Taixing City, Jiangsu province 225453 seven Wei Cun, Taizhou City Road West Patentee before: Jiangsu Zhongdan Group Co., Ltd. Patentee before: Jiangsu Zhongdan Chemical Technology Co., Ltd. Patentee before: Jiangsu Zhongdan Pharmaceutical Research Company Limited |